WO2024004673A1 - Composition adhésive thermofusible, matériau de surface pré-revêtu pour intérieur d'automobile, matériau intérieur d'automobile et procédé de production d'objet lié - Google Patents

Composition adhésive thermofusible, matériau de surface pré-revêtu pour intérieur d'automobile, matériau intérieur d'automobile et procédé de production d'objet lié Download PDF

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Publication number
WO2024004673A1
WO2024004673A1 PCT/JP2023/022213 JP2023022213W WO2024004673A1 WO 2024004673 A1 WO2024004673 A1 WO 2024004673A1 JP 2023022213 W JP2023022213 W JP 2023022213W WO 2024004673 A1 WO2024004673 A1 WO 2024004673A1
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Prior art keywords
weight
melt adhesive
hot melt
less
adhesive composition
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PCT/JP2023/022213
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English (en)
Japanese (ja)
Inventor
英之 小▲柳▼
雁妹 張
誠治 桂
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サンスター技研株式会社
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Publication of WO2024004673A1 publication Critical patent/WO2024004673A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/40—Applying molten plastics, e.g. hot melt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated

Definitions

  • the present disclosure relates to a hot melt adhesive composition, a precoated skin material for automobile interiors using the same, and an automobile interior material.
  • Hot melt adhesives are solid at room temperature, are heated and melted and applied to base materials, and are cooled and solidified to bond the base materials together. Hot melt adhesives have advantages over solvent-based adhesives, such as reduced VOC and improved productivity due to the omission of a drying process, and are used in various applications, such as automobile manufacturing.
  • Patent Document 1 discloses a hot melt adhesive composition containing a hydrocarbon-based cyclic polymer, an ⁇ -olefin-based polymer, and a tackifier resin.
  • Patent Document 2 describes an ⁇ -olefin copolymer polymerized using a multi-site catalyst, an ⁇ -olefin copolymer polymerized using a single-site catalyst, an ethylene-polar group-containing monomer copolymer, and a hydrogenated
  • a hot melt adhesive composition is disclosed that includes a polypropylene-based tackifying resin and a polypropylene-based wax in specific proportions.
  • Patent Document 1 and Patent Document 2 do not discuss the process of peeling the hot melt adhesive from the mold.
  • Conventional hot melt adhesives take time to solidify from a molten state, and during that time, the hot melt adhesive cannot be easily peeled from the mold, resulting in poor workability. Additionally, when conventional hot melt adhesives are used, there are problems from a workability perspective, as the hot melt adhesive remains after being peeled off from the mold, requiring manual peeling and cleaning. It can be.
  • the present disclosure provides a hot melt that has good adhesion to resin base materials, particularly polyolefin base materials such as polypropylene, and also has workability (mold releasability) that allows it to be easily peeled from a mold.
  • resin base materials particularly polyolefin base materials such as polypropylene
  • workability molding releasability
  • the purpose is to provide adhesives.
  • the crystalline polyolefin (A) contains an ethylene-propylene copolymer.
  • the amorphous polyolefin (B) has a softening point of 100° C. or higher.
  • the amorphous polyolefin (B) contains at least one selected from the group consisting of an ethylene-propylene binary copolymer and an ethylene-propylene-butene ternary copolymer.
  • [Section 6] Item 6.
  • Item 7 The hot melt adhesive composition according to any one of Items 1 to 6, comprising a tackifier (D).
  • the tackifier (D) has a softening point of 90°C or higher.
  • the tackifier (D) contains at least one selected from the group consisting of hydrogenated petroleum resins, terpene resins, and terpene phenol resins.
  • the tackifier (D) contains at least one selected from the group consisting of hydrogenated petroleum resins, terpene resins, and terpene phenol resins.
  • [Section 15] A skin material for automotive interiors, and a hot melt adhesive layer formed from the hot melt adhesive composition according to any one of Items 1 to 14 on the back side of the skin material for automotive interiors. Pre-coated skin material.
  • [Section 16] An automobile interior material comprising an automobile interior molded article and the precoated skin material for automobile interior according to item 15, which is adhered to the automobile molded article via the hot melt adhesive layer.
  • [Section 17] A method for manufacturing an adhesive body, the method comprising: The adhesive body is adhered to the first base material through a first base material and a hot melt adhesive layer formed from the hot melt adhesive composition according to any one of Items 1 to 14. having a second base material, A method for producing an adhesive body, comprising a step of bringing a mold into contact with the hot melt adhesive composition.
  • the hot melt adhesive of the present disclosure has particularly good adhesion to polyolefin substrates such as polypropylene, and also has good mold releasability and is excellent in workability.
  • the hot melt adhesive composition of the present disclosure includes a crystalline polyolefin (A), an amorphous polyolefin (B), and a polypropylene wax (C).
  • the hot melt adhesive composition of the present disclosure may optionally contain a tackifier (D), an antioxidant (E), an inorganic filler (F), an elastomer ( G), a plasticizer (H), and other additives (I).
  • the hot melt adhesive composition of the present disclosure includes a crystalline polyolefin (A).
  • the crystalline polyolefin (A) is a polyolefin with high crystallinity. Crystalline polyolefin (A) is distinguished from other components described herein in terms of crystallinity, Shore A hardness, and/or molecular weight. Typically, the crystallinity of the crystalline polyolefin (A) is 20% or more. Typically, the Shore A hardness of the crystalline polyolefin (A) is 80 or higher. Typically, the crystalline polyolefin (A) has a weight average molecular weight of 40,000 or more.
  • the degree of crystallinity of the crystalline polyolefin (A) may be 20% or more, 25% or more, 30% or more, or 35% or more.
  • the crystallinity of the crystalline polyolefin (A) may be 100% or less, 98% or less, 95% or less, 90% or less, or 85% or less. It is preferable that the degree of crystallinity is equal to or higher than the above lower limit value from the viewpoint of better achieving the effects of the present disclosure.
  • the degree of crystallinity can be measured, for example, by differential scanning calorimetry, polymer X-ray diffraction, or the like.
  • crystalline in the present disclosure may mean a property in which a clear endothermic peak originating from a crystalline portion is observed in differential scanning calorimetry, while “amorphous” refers to In measurement, it may also mean the property that no clear endothermic peak originating from the crystalline portion is observed.
  • the Shore A hardness of the crystalline polyolefin (A) may be 80 or more, 85 or more, 90 or more, or 95 or more, preferably 85 or more, and more preferably 90 or more.
  • the Shore A hardness of the crystalline polyolefin (A) may be 100 or less, 99 or less, 98 or less, or 97 or less.
  • Shore A hardness can be used as an indicator of the cohesive force of a resin, and can be one of the indicators of adhesiveness at room temperature and hot. It is preferable that the content be within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • the melting point of the crystalline polyolefin (A) may be 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, or 110°C or higher, preferably 80°C or higher.
  • the melting point of the crystalline polyolefin (A) may be 150°C or lower, 140°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, or 90°C or lower, preferably 120°C or lower, for example 110°C or lower. °C or lower, or 100°C or lower. It is preferable that the content be within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • the glass transition temperature of the crystalline polyolefin (A) may be -150°C or higher, -125°C or higher, -100°C or higher, -75°C or higher, -50°C or higher, or -25°C or higher.
  • the glass transition temperature of the crystalline polyolefin (A) may be 20°C or lower, 10°C or lower, 0°C or lower, -10°C or lower, or -20°C or lower, preferably 0°C or lower, more preferably -10°C. It is as follows. It is also preferable from the viewpoint of low-temperature adhesion that the glass transition temperature is below the above upper limit.
  • the crystalline polyolefin (A) is typically thermoplastic.
  • the MFR of the crystalline polyolefin (A) may be 3 g/10 minutes or more, 5 g/10 minutes or more, 7 g/10 minutes or more, 10 g/10 minutes or more, 12 g/10 minutes or more, or 15 g/10 minutes or more, Preferably it is 5 g/10 minutes or more, more preferably 7 g/10 minutes or more.
  • the MFR of the crystalline polyolefin (A) may be 40 g/10 minutes or less, 30 g/10 minutes or less, 20 g/10 minutes or less, 15 g/10 minutes or less, or 10 g/10 minutes or less. It is preferable that the MFR is in a range equal to or higher than the above lower limit from the viewpoint of low melt viscosity and coating stability. MFR can be measured based on JIS K7210.
  • the weight average molecular weight of the crystalline polyolefin (A) may be 40,000 or more, 50,000 or more, 75,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 500,000 or more. , 100,000 or more is preferred.
  • the weight average molecular weight of the crystalline polyolefin (A) is 5,000,000 or less, 2,000,000 or less, 1,500,000 or less, 1,200,000 or less, 1,000,000 or less, 800,000 or less , 600,000 or less, 400,000 or less, or 200,000 or less, preferably 1,000,000 or less, such as 600,000 or less. It is preferable that the weight average molecular weight is within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • Crystalline polyolefin (A) is a polymer having repeating units derived from olefins.
  • the crystalline polyolefin (A) is preferably an ⁇ -olefin polymer having repeating units derived from an ⁇ -olefin, particularly an ⁇ -olefin copolymer.
  • the crystalline polyolefin (A) may be a homopolymer, a copolymer, or a mixture thereof.
  • the form of the copolymer may be random copolymerization, block copolymerization, graft copolymerization, or the like.
  • repeating units contained in the crystalline polyolefin (A) include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1 - Derived from nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, etc. These repeating units may be used alone or in combination of two or more.
  • the crystalline polyolefin (A) preferably contains repeating units derived from propylene among the above-mentioned repeating units, for example repeating units derived from propylene and repeating units derived from other ⁇ -olefins (e.g. ethylene). May contain both units and.
  • the repeating units constituting the crystalline polyolefin (A) are 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% % or more, preferably 30 mol% or more.
  • the crystalline polyolefin (A) include ethylene homopolymer, propylene homopolymer, ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, and ethylene-1-octene.
  • Examples include copolymers of olefins such as copolymers, ethylene-1-hexene copolymers, and ethylene-propylene-1-butene copolymers, and preferred examples include ethylene-propylene copolymers. These may be used alone or in combination of two or more.
  • Examples of typical commercially available crystalline polyolefins (A) include the product names "Tafmer XM-7090", “Tafmer XM-7080", “Tafmer XM-7070”, and “Tafmer , Tafmar series such as “Tafmar XM-5080", “Tafmar XM-5070", “Tafmar BL-2491M”, “Tafmar DF110”; , ExxonMobil's Vistamaxx series such as “Vistamaxx8880", “Vistamaxx3000", and “Vistamaxx3980FL”, and Idemitsu Kosan's "L-MODU S901", “L-MODU S600", “L-MODU S400”, etc. It will be done.
  • the crystalline polyolefin (A) may be used alone or in combination of two or more types.
  • the hot melt adhesive composition of the present disclosure includes an amorphous polyolefin (B).
  • the amorphous polyolefin (B) is a polyolefin that does not have crystallinity or has a small amount of crystallinity, and can impart flexibility.
  • the amorphous polyolefin (B) is distinguished from other components described herein in terms of crystallinity, molecular weight, and the like.
  • the crystallinity of the amorphous polyolefin (B) is less than 20%.
  • the amorphous polyolefin (B) has a weight average molecular weight of 40,000 or more.
  • the degree of crystallinity of the amorphous polyolefin (B) may be 0% or more, 3% or more, or 5% or more.
  • the crystallinity of the amorphous polyolefin (B) may be less than 20%, 15% or less, 10% or less, 5% or less, 3% or less, or 1% or less. It is preferable that the degree of crystallinity is less than or equal to the above upper limit value from the viewpoint of better achieving the effects of the present disclosure.
  • the degree of crystallinity can be measured, for example, by differential scanning calorimetry, polymer X-ray diffraction, or the like.
  • the softening point of the amorphous polyolefin (B) may be 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, or 130°C or higher, preferably 80°C or higher,
  • the temperature is 100°C or higher.
  • the softening point of the amorphous polyolefin (B) may be 180°C or lower, 170°C or lower, 160°C or lower, 150°C or lower, 140°C or lower, 130°C or lower, 120°C or lower, or 110°C or lower, preferably
  • the temperature is 160°C or lower, for example 140°C or lower. It is preferable that the content be within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • the softening point can be measured by the ring and ball method.
  • the glass transition temperature of the amorphous polyolefin (B) may be -150°C or higher, -125°C or higher, -100°C or higher, -75°C or higher, -50°C or higher, or -25°C or higher.
  • the glass transition temperature of the crystalline polyolefin (A) may be 20°C or lower, 10°C or lower, 0°C or lower, -10°C or lower, or -20°C or lower, preferably 0°C or lower, more preferably -10°C. It is as follows. It is also preferable from the viewpoint of low-temperature adhesion that the glass transition temperature is below the above upper limit.
  • the amorphous polyolefin (B) is typically thermoplastic.
  • the MFR of the amorphous polyolefin (B) may be 3 g/10 minutes or more, 5 g/10 minutes or more, 7 g/10 minutes or more, 10 g/10 minutes or more, 12 g/10 minutes or more, or 15 g/10 minutes or more. , preferably 5 g/10 minutes or more, more preferably 7 g/10 minutes or more.
  • the MFR of the amorphous polyolefin (B) may be 40 g/10 minutes or less, 30 g/10 minutes or less, 20 g/10 minutes or less, 15 g/10 minutes or less, or 10 g/10 minutes or less. It is preferable that the MFR is in a range equal to or higher than the above lower limit from the viewpoint of low melt viscosity and coating stability. MFR can be measured based on JIS K7210.
  • the weight average molecular weight of the amorphous polyolefin (B) is 40,000 or more, 50,000 or more, 75,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 500,000 or more. Generally, 100,000 or more is preferred.
  • Amorphous polyolefin (B) is 5,000,000 or less, 2,000,000 or less, 1,500,000 or less, 1,200,000 or less, 1,000,000 or less, 800,000 or less, 600, 000 or less, 400,000 or less, or 200,000 or less, preferably 1,000,000 or less, such as 600,000 or less. It is preferable that the weight average molecular weight is within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • the amorphous polyolefin (B) is a polymer having repeating units derived from olefins.
  • the amorphous polyolefin (B) is preferably an ⁇ -olefin polymer having repeating units derived from an ⁇ -olefin, particularly an ⁇ -olefin copolymer.
  • the amorphous polyolefin (B) may be a homopolymer, a copolymer, or a mixture thereof.
  • the form of the copolymer may be random copolymerization, block copolymerization, graft copolymerization, or the like.
  • repeating units contained in the amorphous polyolefin (B) include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, From 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene, etc. Examples include derived repeating units, and these may be used alone or in combination of two or more.
  • the amorphous polyolefin (B) preferably contains repeating units derived from propylene among the above-mentioned repeating units, for example, repeating units derived from propylene and other repeating units derived from ⁇ -olefins (e.g. ethylene). It may contain both repeating units and.
  • the repeating units constituting the amorphous polyolefin (B) are 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more It may be mol% or more, preferably 30 mol% or more.
  • amorphous polyolefin (B) examples include ethylene homopolymer, propylene homopolymer, ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1- Examples include copolymers of olefins such as octene copolymers, ethylene-1-hexene copolymers, and ethylene-propylene-1-butene copolymers; preferred examples include ethylene-propylene binary copolymers. and/or a terpolymer of ethylene-propylene-butene. These may be used alone or in combination of two or more.
  • Examples of typical commercially available amorphous polyolefins include the product names "Bestplast 308", “Bestplast 508", “Bestplast 520", “Bestplast 608", and “Bestplast” manufactured by Evonik.
  • RT series such as product names "RT2280", “RT2385”, “RT2585”, and “RT2780” manufactured by REXtac.
  • the hot melt adhesive composition of the present disclosure includes a polypropylene wax (C).
  • Polypropylene wax (C) is a wax having repeating units derived from propylene.
  • the polypropylene wax (C) generally has a low molecular weight (less than 40,000), and can impart coatability and wettability to adherends by lowering the viscosity of the hot melt adhesive. Further, the polypropylene wax (C) can promote crystallization and solidification of the crystalline polyolefin (A), improve the solidification rate of the hot melt adhesive, and improve mold releasability.
  • the softening point of the polypropylene wax (C) is 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, or 150°C or higher, preferably 110°C or higher, more preferably 120°C.
  • the temperature is above, more preferably 130°C or above.
  • the softening point of the polypropylene wax (C) may be 220°C or lower, 210°C or lower, 190°C or lower, 180°C or lower, 170°C or lower, 160°C or lower, or 150°C or lower, preferably 190°C or lower, e.g.
  • the temperature is 160°C or less.
  • the content be within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • the softening point can be measured by the ring and ball method. It is preferable that the softening point of the polypropylene wax (C) is below the above upper limit because the melting temperature can be set low and the working time can be shortened.
  • the weight average molecular weight of the polypropylene wax (C) may be 3,000 or more, 5,000 or more, or 7,000 or more, preferably 3,000 or more.
  • the weight average molecular weight of the polypropylene wax (C) may be less than 40,000, 35,000 or less, 30,000 or less, 20,000 or less, or 10,000 or less, preferably 20,000 or less. It is preferable that the weight average molecular weight is within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • the polypropylene wax (C) may have repeating units other than repeating units derived from propylene, such as repeating units derived from ⁇ -olefin.
  • the polypropylene wax (C) may be a low molecular weight polyolefin, particularly a low molecular weight ⁇ -olefin polymer.
  • the polypropylene wax (C) may be a homopolymer, a copolymer, or a mixture thereof.
  • the form of the copolymer may be random copolymerization, block copolymerization, graft copolymerization, or the like.
  • repeating units contained in the polypropylene wax (C) other than repeating units derived from propylene include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1- Putene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and repeating units derived from 1-eicosene and the like, which may be used alone or in combination of two or more.
  • the repeating units derived from propylene are 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol%. % or more, preferably 30 mol% or more.
  • Examples of typical commercial products of polypropylene wax (C) include the product names "Viscol 660-P”, “Viscol 550-P”, “Viscol 440-P”, and “Viscol 330-P” manufactured by Sanyo Chemical Industries, Ltd. Viscole series such as ⁇ Hiwax 100P'', ⁇ Hiwax 200P'', ⁇ Hiwax 400P'', ⁇ Hiwax 800P'', ⁇ Hiwax 410P'', ⁇ Hiwax 420P'', etc. manufactured by Mitsui Chemicals.
  • the hot melt adhesive composition of the present disclosure may also include a tackifier (D).
  • the tackifier (D) can improve tackiness when melted.
  • the softening point of the tackifier (D) is 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, or 150°C or higher, preferably 110°C or higher, more preferably 120°C.
  • the temperature is above, more preferably 130°C or above.
  • the softening point of the tackifier (D) may be 220°C or lower, 210°C or lower, 190°C or lower, 180°C or lower, 170°C or lower, 160°C or lower, or 150°C or lower, preferably 190°C or lower, e.g.
  • the temperature is 160°C or less.
  • the content be within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • the softening point can be measured by the ring and ball method. It is preferable that the softening point of the tackifier (D) is below the above upper limit, since the melting temperature can be set low and the working time can be shortened.
  • tackifier (D) examples include rosin resin, rosin ester, disproportionated rosin ester, hydrogenated rosin ester, polymerized rosin, aliphatic hydrocarbon resin, aliphatic aromatic copolymer resin, and aromatic petroleum.
  • tackifier (D) is distinguished from other components such as polyolefin in terms of the presence or absence of intramolecular double bonds, intramolecular polar groups, intramolecular hydrocarbon groups, etc.
  • Examples of typical commercially available tackifiers (D) include the product names "Alcon P-90”, “Alcon P-100”, “Alcon P-115”, and “Alcon P-140” manufactured by Arakawa Chemical Co., Ltd. , “Alcon M-90”, “Alcon M-100”, “Alcon M-115”, “Alcon M-135” and other Alcon series; product names manufactured by Idemitsu Kosan Co., Ltd.
  • YS resin series such as “TO115”, “YS Resin TO105”, “YS Polyster T160”, “YS Polyster T145”, “YS Polyster T130”, “YS Polyster T115”, “YS Polyster T100”, “YS Polyster UH115”, etc.
  • YS polyster series examples include FTR series such as “FTR6100”, “FTR6110", and “FTR6125” manufactured by Mitsui Chemicals.
  • the tackifier (D) may be used alone or in combination of two or more. Furthermore, a tackifier having a softening point of less than 90° C. can be blended within a range that does not impair the desired physical properties.
  • the hot melt adhesive composition of the present disclosure may also include an antioxidant (E).
  • an antioxidant (E) improves thermal stability and may be suitable from the viewpoint of favorably achieving the effects of the present disclosure.
  • antioxidant (E) examples include hindered phenols, polyphenols, bisphenols, phosphates, thioethers, hydrosarites, benzimidazoles, aromatic secondary amines, and the like.
  • antioxidants examples include BASF's product names "Irganox 1010,” “Irganox 1035,” “Irganox 1076,” “Irganox 1098,” and “Irganox 1330.” “, “Irganox 245", “Irganox 259”, “Irganox 3114”, “Irganox 565", “Irganox 168”, etc.
  • ADEKA product name "ADEKA STAB AO-20", " ADEKA STAB AO-30'', ⁇ ADEKA STAB AO-40'', ⁇ ADEKA STAB AO-50'', ⁇ ADEKA STAB AO-60'', ⁇ ADEKA STAB AO-80'', ⁇ ADEKA STAB AO-330'', ⁇ ADEKA STAB PEP-8'', ⁇ ADEKA STAB Examples include the “ADK STAB” series such as "PEP-36", “ADK STAB HP-10", “ADK STAB 2112", “ADK STAB AO-412S", etc.
  • the antioxidant (E) may be used alone or in combination of two or more kinds.
  • the hot melt adhesive composition of the present disclosure may also include an inorganic filler (F).
  • an inorganic filler (F) By adding the inorganic filler (F), it is possible to adjust adhesiveness, sagging properties, specific gravity, etc.
  • inorganic fillers (F) include calcium carbonate (ground calcium carbonate, surface-untreated calcium carbonate, surface-treated calcium carbonate (e.g. fatty acid-treated calcium carbonate, etc.), acicular crystalline calcium carbonate), silica (fume silica), , hydrophobic silica, precipitated silica, etc.), talc, mica (mica), clay, chrysotile, wollastonite, carbon black, graphite, balloons (shirasu balloon, glass balloon, silica balloon, etc.), inorganic fiber (glass fiber) , metal fibers, etc.), titanium oxide, aluminum oxide, aluminum borate, silicon carbide, silicon nitride, potassium titanate, magnesium borate, titanium diboride, aluminum flakes, aluminum powder, iron powder, and the like.
  • the inorganic filler (F) may be used alone or in combination of two or more kinds.
  • the hot melt adhesive composition of the present disclosure may include an elastomer (G).
  • Elastomer (G) is a polymer that exhibits elasticity.
  • the elastomer (G) may be thermoset or thermoplastic, preferably thermoplastic.
  • Elastomer (G) is distinguished from the other components described herein in terms of crystallinity, Shore A hardness, and/or molecular weight.
  • the elastomer (G) is not amorphous.
  • the elastomer (G) has a Shore A hardness of less than 80.
  • the elastomer (G) has a weight average molecular weight of 40,000 or more.
  • the Shore A hardness of the elastomer (G) may be 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, or 70 or more, preferably 40 or more.
  • the Shore A hardness of the elastomer (G) may be less than 80, 75 or less, 70 or less, 65 or less, or 60 or less. It is preferable that the Shore A hardness of the elastomer (G) is within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • the MFR of the elastomer (G) may be 3 g/10 minutes or more, 5 g/10 minutes or more, 7 g/10 minutes or more, 10 g/10 minutes or more, 12 g/10 minutes or more, or 15 g/10 minutes or more, preferably It is 5 g/10 minutes or more, more preferably 7 g/10 minutes or more.
  • the MFR of the elastomer (G) may be 40 g/10 minutes or less, 30 g/10 minutes or less, 20 g/10 minutes or less, 15 g/10 minutes or less, or 10 g/10 minutes or less. It is preferable that the MFR is in a range equal to or higher than the above lower limit from the viewpoint of low melt viscosity and coating stability. MFR can be measured based on JIS K7210.
  • the weight average molecular weight of the elastomer (G) may be 40,000 or more, 50,000 or more, 75,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 500,000 or more; ,000 or more is preferable.
  • the weight average molecular weight of the elastomer (G) is 5,000,000 or less, 2,000,000 or less, 1,500,000 or less, 1,200,000 or less, 1,000,000 or less, 800,000 or less, 600 ,000 or less, 400,000 or less, or 200,000 or less, preferably 1,000,000 or less, such as 600,000 or less. It is preferable that the weight average molecular weight is within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • elastomer (G) examples include rubber elastomer, olefin elastomer, styrene elastomer (for example, hydrogenated or non-hydrogenated styrene elastomer), vinyl chloride elastomer, urethane elastomer, ester elastomer, and amide elastomer. etc. From the viewpoint of compatibility, olefin elastomers are preferred.
  • the olefinic elastomer may be an olefinic elastomer having repeating units derived from propylene.
  • elastomer (G) examples include the Tafmer PN series, such as Mitsui Chemicals' product name “Tafmer PN-2070” and “Tafmer PN-3560”; the Dow Chemical Company's product name “INFUSE9807”; ”, “INFUSE9817”, “INFUSE9990”, and the Vistamaxx series, such as “Vistamaxx6502” and “Vistamaxx6202” manufactured by ExxonMobil.
  • the elastomer (G) may be used alone or in combination of two or more.
  • the hot melt adhesive composition of the present disclosure may also include a plasticizer (H).
  • the plasticizer (H) is an oily substance such as a low molecular weight compound containing a chain alkyl group or an olefin oligomer.
  • the plasticizer (H) can improve the applicability and wettability to adherends by lowering the viscosity of the hot melt adhesive.
  • the weight average molecular weight of the plasticizer (H) may be 100 or more, 300 or more, or 500 or more.
  • the weight average molecular weight of the plasticizer (H) may be less than 3000, 2500 or less, 20000 or less, 1500 or less, or 1000 or less, preferably 2000 or less. It is preferable that the weight average molecular weight is within the above range from the viewpoint of better achieving the effects of the present disclosure.
  • plasticizer (H) examples include liquid paraffin, process oil, phthalic acid plasticizer, butene oligomer, butadiene oligomer, liquid ethylene/propylene oligomer, liquid rubber, etc. From the viewpoint of compatibility, Butene oligomers or liquid ethylene/propylene oligomers are preferred.
  • plasticizers (H) examples include “NOF Polybutene 0N”, “NOF Polybutene 015N”, “NOF Polybutene 3N”, “NOF Polybutene 10N”, and “NOF Polybutene 10N” manufactured by NOF Corporation.
  • Polybutene series such as “Oil Polybutene 30N” and “NOF Polybutene 200N”; "Lucant LX004", “Lucant LX010", “Lucant LX020”, “Lucant LX100”, “Lucant LX200”, “Lucant LX400” manufactured by Mitsui Chemicals , Lucant series such as “Lucant LX900Z”, etc.
  • the plasticizer (H) may be used alone or in combination of two or more kinds.
  • Adhesives silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, aminosilane, mercaptosilane, epoxysilane, etc., glycidyl having a polyoxyalkylene skeleton
  • Vulcanization accelerators guanidines, aldehyde-amines, aldehyde-ammonias, thiazoles, sulfenamides, thioureas, thiurams, dithiocarbamates, xanthates, etc.
  • Vulcanization aids long-chain fatty acids with 12 or more carbon atoms such as stearic acid, oleic acid, and palmitic acid; metal oxides such as zinc oxide, magnesium oxide, and lead oxide); anti-aging agents (hindered phenols, mercaptans, sulfides,
  • the hot melt adhesive composition of the present disclosure may be solvent-free and may not contain a solvent.
  • the hot melt adhesive composition of the present disclosure may be non-reactive and may not contain reactive additives.
  • the amount of crystalline polyolefin (A) is 2.5% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% by weight or more, 15% by weight or more in the hot melt adhesive composition. It may be at least 17.5% by weight, at least 20% by weight, at least 22.5% by weight, or at least 25% by weight, preferably at least 10% by weight, more preferably at least 15% by weight.
  • the amount of crystalline polyolefin (A) is 40% by weight or less, 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, or 15% by weight or less in the hot melt adhesive composition. The amount may be 30% by weight or less, preferably 30% by weight or less.
  • the amount of amorphous polyolefin (B) in the hot melt adhesive composition is 2.5% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% by weight or more, It may be 15% by weight or more, 17.5% by weight or more, 20% by weight or more, 22.5% by weight or more, or 25% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more. .
  • the amount of amorphous polyolefin (B) is 40% by weight or less, 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, or 15% by weight or less in the hot melt adhesive composition. It may be present, preferably 30% by weight or less.
  • the amount of polypropylene wax (C) is 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight in the hot melt adhesive composition. % or more, 45 weight % or more, or 50 weight % or more, preferably 20 weight % or more, more preferably 30 weight % or more.
  • the amount of polypropylene wax (C) is 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, 50% by weight or less, or 45% by weight or less in the hot melt adhesive composition. It may be up to 65% by weight, more preferably up to 50% by weight.
  • the amount of the tackifier (D) is 2.5% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% by weight or more, 15% by weight or more in the hot melt adhesive composition. It may be at least 17.5% by weight, at least 20% by weight, at least 22.5% by weight, or at least 25% by weight, preferably at least 10% by weight, more preferably at least 15% by weight.
  • the amount of tackifier (D) is 40% by weight or less, 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, or 15% by weight or less in the hot melt adhesive composition. The amount may be 30% by weight or less, preferably 30% by weight or less.
  • the amount of the inorganic filler (F) is 1% by weight or more, 2.5% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% by weight or more in the hot melt adhesive composition. It may be at least 15% by weight, preferably at least 2.5% by weight, more preferably at least 5% by weight.
  • the amount of the inorganic filler (F) is 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less in the hot melt adhesive composition. It's fine.
  • the amount of elastomer (G) is 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, 4% by weight or more, 5% by weight or more, 6% by weight in the hot melt adhesive composition. % or more, 7 weight % or more, 8 weight % or more, 9 weight % or more, or 10 weight % or more, preferably 1 weight % or more, more preferably 3 weight % or more.
  • the amount of elastomer (G) in the hot melt adhesive composition is 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5% by weight or less, or 2% by weight or less. It may be up to .5% by weight, preferably up to 15% by weight, more preferably up to 10% by weight.
  • the amount of the other component (I) in the hot melt adhesive composition of the present disclosure may be appropriately selected depending on each component.
  • the total amount of other components (I) in the hot melt adhesive composition is 0.1% by weight or more, 0.2% by weight or more, 0.5% by weight or more, 1% by weight or more, 2.5% by weight or more, Or it may be 5% by weight or more.
  • the total amount of other components (I) in the hot melt adhesive composition is 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or It may be 5% by weight or less, 2.5% by weight or less, or 1% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less.
  • the respective amounts of other components (I) are 0.01% by weight or more, 0.05% by weight or more, 0.1% by weight or more, 0.3% by weight or more, and 0.5% by weight in the hot melt adhesive composition. % or more, 0.75% or more, 1% or more by weight, or 2.5% or more by weight. Further, the amount of each of the other components (I) in the hot melt adhesive composition is 10% by weight or less, 7.5% by weight or less, 5% by weight or less, 2.5% by weight or less, or 1% by weight or less. It's good to be there.
  • the amount of plasticizer (H) may be based on the amount of other component (I).
  • the total amount of crystalline polyolefin (A) and amorphous polyolefin (B) is 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight in the hot melt adhesive composition. % or more, 30 wt.% or more, 35 wt.% or more, 40 wt.% or more, 45 wt.% or more, or 50 wt.% or more, preferably 20 wt.% or more, more preferably 30 wt.% or more.
  • the total amount of crystalline polyolefin (A) and amorphous polyolefin (B) is 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight in the hot melt adhesive composition. % or less, or 30% by weight or less, preferably 60% by weight or less. Being within the above range is preferable from the viewpoint of achieving the effects of the present disclosure favorably.
  • the amount of crystalline polyolefin (A) is 15 parts by weight or more, 25 parts by weight or more, more than 50 parts by weight, 75 parts by weight or more, 100 parts by weight or more with respect to 100 parts by weight of the amorphous polyolefin (B). , 125 parts by weight or more, 150 parts by weight or more, preferably 25 parts by weight or more, more preferably 60 parts by weight or more, still more preferably 75 parts by weight or more.
  • the amount of crystalline polyolefin (A) is 500 parts by weight or less, 450 parts by weight or less, 400 parts by weight or less, 350 parts by weight or less, 300 parts by weight or less, based on 100 parts by weight of the amorphous polyolefin (B).
  • 200 parts by weight or less 150 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, or 50 parts by weight or less, preferably 400 parts by weight or less, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less. Parts by weight or less. Being within the above range is preferable from the viewpoint of achieving the effects of the present disclosure favorably.
  • the amount of polypropylene wax (C) is more than 50 parts by weight, 60 parts by weight or more, 70 parts by weight or more, based on 100 parts by weight of the total amount of crystalline polyolefin (A) and amorphous polyolefin (B).
  • the amount may be 80 parts by weight or more, 90 parts by weight or more, 100 parts by weight or more, 110 parts by weight or more, or 120 parts by weight or more, preferably 60 parts by weight or more, more preferably 80 parts by weight or more, and even more preferably It is 90 parts by weight or more.
  • the amount of polypropylene wax (C) is 350 parts by weight or less, 300 parts by weight or less, 250 parts by weight or less, based on 100 parts by weight of the total amount of crystalline polyolefin (A) and amorphous polyolefin (B).
  • the amount may be 200 parts by weight or less, 150 parts by weight or less, or 100 parts by weight or less, preferably 300 parts by weight or less, more preferably 250 parts by weight or less, still more preferably 200 parts by weight or less.
  • Being within the above range is preferable from the viewpoint of achieving the effects of the present disclosure favorably.
  • the crystallization promoting effect can be improved and the mold releasability can be improved.
  • adhesiveness can be improved.
  • the amount of the tackifier (D) is 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, based on 100 parts by weight of the total amount of the crystalline polyolefin (A) and the amorphous polyolefin (B).
  • the amount may be 40 parts by weight or more, 50 parts by weight or more, or 60 parts by weight or more, preferably 20 parts by weight or more, and more preferably 40 parts by weight or more.
  • the amount of the tackifier (D) is 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, based on 100 parts by weight of the total amount of the crystalline polyolefin (A) and the amorphous polyolefin (B).
  • the amount may be 75 parts by weight or less, 50 parts by weight or less, or 30 parts by weight or less, preferably 100 parts by weight or less, more preferably 75 parts by weight or less. It is preferable that the content be within the above range from the viewpoint of achieving the effects of the present disclosure favorably.
  • the amount of the inorganic filler (F) is 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, based on 100 parts by weight of the total amount of the crystalline polyolefin (A) and the amorphous polyolefin (B).
  • the amount may be 20 parts by weight or more, 25 parts by weight or more, or 30 parts by weight or more, preferably 10 parts by weight or more, more preferably 20 parts by weight or more.
  • the amount of the inorganic filler (F) is 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, based on 100 parts by weight of the total amount of the crystalline polyolefin (A) and the amorphous polyolefin (B).
  • the amount may be 40 parts by weight or less, 30 parts by weight or less, or 20 parts by weight or less, preferably 60 parts by weight or less, more preferably 40 parts by weight or less. Being within the above range is preferable from the viewpoint of achieving the effects of the present disclosure favorably.
  • the amount of the elastomer (G) is 0.5 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, based on 100 parts by weight of the total amount of the crystalline polyolefin (A) and the amorphous polyolefin (B).
  • the amount may be 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, 12 parts by weight or more, or 15 parts by weight or more, preferably 3 parts by weight or more, and more preferably 10 parts by weight or more.
  • the amount of elastomer (G) is 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight based on 100 parts by weight of the total amount of crystalline polyolefin (A) and amorphous polyolefin (B). parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, or 10 parts by weight or less, preferably 40 parts by weight or less, more preferably 20 parts by weight or less. Being within the above range is preferable from the viewpoint of achieving the effects of the present disclosure favorably.
  • the hot melt adhesive composition of the present disclosure has a melt viscosity of 5,000 mPa ⁇ s or more, 7,500 mPa ⁇ s or more, or 10,000 mPa ⁇ s or more at 180° C., which is a common coating temperature for hot melt adhesives. , 12,000 mPa ⁇ s or more, 15,000 mPa ⁇ s or more, 20,000 mPa ⁇ s or more, or 25,000 mPa ⁇ s or more, preferably 10,000 mPa ⁇ s or more, more preferably 15,000 mPa or more It is.
  • the hot melt adhesive composition of the present disclosure has a melt viscosity of 200,000 mPa ⁇ s or less, 150,000 mPa ⁇ s or less, or 100,000 mPa ⁇ s or less at 180° C., which is a common coating temperature for hot melt adhesives. , 50,000 mPa ⁇ s or less, 30,000 mPa ⁇ s or less, or 20,000 mPa ⁇ s or less, preferably 150,000 mPa ⁇ s or less, more preferably 100,000 mPa ⁇ s or less. It is preferable that the melt viscosity is within the above range because dripping, uneven coating, etc. will not occur when applying to an adherend.
  • the above melt viscosity is a value measured using a parallel plate type rheometer at a shear rate of 4.3 sec -1 .
  • the storage modulus at 60°C is 1 ⁇ 10 4 Pa or more, 5 ⁇ 10 4 Pa or more, 1 ⁇ It may be 10 5 Pa or more, 5 ⁇ 10 5 Pa or more, 1 ⁇ 10 6 Pa or more, 2 ⁇ 10 6 Pa or more, or 3 ⁇ 10 6 Pa or more, preferably 1 ⁇ 10 5 Pa or more, more preferably It is 1 ⁇ 10 6 Pa or more.
  • the storage modulus at 60°C is 1 ⁇ 10 8 Pa or less, 5 ⁇ 10 7 Pa or less, 1 ⁇ It may be 10 7 Pa or less, 5 ⁇ 10 6 Pa or less, 3 ⁇ 10 6 Pa or less, or 1 ⁇ 10 6 Pa or less.
  • the above storage modulus is a value measured using a parallel plate rheometer at a shear rate of 4.3 sec -1 .
  • the temperature at which tan ⁇ becomes 1 or less is 30°C or higher, 40°C or higher, 50°C or higher, or 60°C or higher. , or 70°C or higher, preferably 40°C or higher, more preferably 60°C or higher.
  • the temperature at which tan ⁇ becomes 1 or less is 100°C or lower, 90°C or lower, 80°C or lower, or 70°C.
  • the temperature may be below, preferably 80°C or below.
  • tan ⁇ is a loss tangent, and is the ratio of the storage shear modulus (G') to the loss shear modulus (G''), G''/G'.
  • tan ⁇ is a value measured using a parallel plate rheometer at a shear rate of 4.3 sec ⁇ 1 .
  • the hot melt adhesive composition of the present disclosure can be produced by mixing (A) to (C).
  • the hot melt adhesive composition can be produced by mixing (A) to (C) together with other components as necessary using a heating mixer.
  • the adhesive body of the present disclosure has a first base material and a second base material adhered to the first base material via a hot melt adhesive layer formed from a hot melt adhesive composition.
  • the base materials used as the first base material and the second base material are not particularly limited, and include, for example, wood materials; plastic materials such as polyolefin, polyvinyl chloride, polyurethane, polyester, and epoxy resin; foamed materials of the above plastic materials; Materials include: rubber materials such as natural rubber and synthetic rubber; metal materials such as aluminum, iron, and stainless steel; and inorganic materials such as ceramics.
  • the shape of each base material is also not particularly limited, and may be, for example, sheet-like, foil-like, plate-like, or molded. Further, each base material may be made of only one kind of material, or may be made of two or more kinds of materials.
  • the material of the surface of the base material on which the adhesive layer is provided is preferably a non-metal, more preferably a resin as described above, and still more preferably a polyolefin including polypropylene.
  • various hot melt applicators can be used as a method for coating the substrate, and examples include methods using a spray gun, comma coater, die coater, roll coater, and the like.
  • a spray gun When applying to a substrate, it is usually heated at a temperature of 140° C. to 200° C. to melt it, and it can be applied in a molten state.
  • After applying it to a release film or paper it may be used by thermally transferring it to another base material.
  • the hot melt adhesive layer may be solidified on the substrate by cooling.
  • the precoated base material (adhesive layer-containing base material) obtained after the coating process may be used as is for the next molding process, or it can be stored and then used for the next process.
  • the hot melt adhesive layer may be heated and activated to melt it again.
  • means for thermal activation include methods using heating, ultrasound, high frequency, microwave, etc., but there are no particular limitations.
  • the reactivation is performed immediately before the pre-coated base material and the second base material are pressed together.
  • the pre-coated base material and the second base material are pressed together before the surface of the hot melt adhesive composition layer is solidified.
  • the second base material may or may not be heated. Further, as long as the hot-melt adhesive composition layer is in a reactivated state, it is not necessary to heat it at the time of pressure bonding, but it may be heated at the same time as the pressure is applied, if necessary.
  • the temperature for heat activation is preferably 100 to 200°C, for example 100 to 180°C, more preferably 120 to 160°C, based on the surface temperature of the hot melt adhesive layer.
  • the pressure during pressure bonding for adhesion between the first base material and the second base material may be 0.01 to 0.5 MPa, preferably 0.01 to 0.20 MPa, and more preferably 0.01 to 0.10 MPa. preferable.
  • the time for pressure bonding may be, for example, 1 to 300 seconds, preferably 1 to 60 seconds, and more preferably 10 to 30 seconds.
  • the method for manufacturing an adhesive body of the present disclosure includes a step in which a mold and a hot melt adhesive composition are brought into contact with each other.
  • the mold and the hot melt adhesive composition may be in contact with each other during the coating process or the bonding process.
  • the method for producing an adhesive body of the present disclosure can be suitably used in a vacuum forming method that includes a step in which a mold and a hot melt adhesive composition are brought into contact.
  • the material of the mold is not limited, but may be made of metal, ceramic, etc., and is preferably made of metal (for example, various alloys such as aluminum, iron, stainless steel, etc.).
  • the method for producing an adhesive body of the present disclosure may further include the step of peeling off the hot melt adhesive layer formed from the hot melt adhesive composition from the mold.
  • the hot melt adhesive layer may be peeled off from the mold after cooling.
  • the automobile interior material of the present disclosure includes an automobile interior molded article and an automobile interior adhered to the automobile interior molded article through a hot melt adhesive layer formed from the hot melt adhesive composition of the present disclosure. (hereinafter also referred to as "skin material").
  • the skin material may be a skin material derived from a hot melt adhesive layer-containing skin material (pre-coated skin material). Examples of automobile interior materials include door trims, instrument panels, ceiling materials, rear trays, pillars, and the like.
  • molded products for automobile interiors there are no particular restrictions on the material for molded products for automobile interiors, as long as they are used for automobile interior materials, such as wood materials such as paper and wood; polyolefins (polypropylene, polyethylene, ethylene-propylene copolymer, etc.), Plastic materials such as polyvinyl chloride, polyurethane, polyester, epoxy resin, nylon, polyester, polycarbonate, polyurethane, acrylic, ABS, and PCABS; Rubber materials such as natural rubber and synthetic rubber; Metal materials such as aluminum, iron, and stainless steel; Examples include inorganic materials such as ceramics. Molded products for automobile interiors may be made of only one kind of material, or may be made of two or more kinds of materials.
  • the material of the surface of the molded article for automobile interiors on which the adhesive layer is provided is preferably the above-mentioned molded article material for automobile interiors that is non-metallic, and more preferably the above-mentioned molded article material for automobile interiors that is made of resin.
  • Polyolefins such as polypropylene are more preferred.
  • the skin material is not particularly limited as long as it is a material used for automobile interior materials, such as plastic sheets such as polyolefin, soft polyvinyl chloride, and polyurethane; foams of the above plastics; rubbers such as natural rubber and synthetic rubber. Sheets; fabric materials such as woven fabrics and non-woven fabrics; metal foils such as aluminum, and the like.
  • the skin material may consist of only one layer, or may include two or more layers of the same kind of material or different materials.
  • a skin material containing two or more types of layers includes, for example, one or more layers of the above-mentioned plastic sheet, rubber sheet, fabric material, metal foil, etc., and one or more types of the above-mentioned plastic foam. Examples include sheet materials with laminated layers.
  • laminated sheet materials include flexible polyvinyl chloride with polyolefin foam, olefinic thermoplastic elastomer with polyolefin foam, fabric with polyurethane foam, and the like.
  • the material of the surface on which the adhesive layer of the skin material is provided is preferably the skin material mentioned above which is non-metallic, more preferably the skin material mentioned above which is made of resin, and still more preferably polypropylene or the like. It is a polyolefin.
  • the method for producing an automobile interior material of the present disclosure includes the method for producing an adhesive body described above, wherein the adhesive body is an automobile interior material, the first base material is a skin material, and the second base material is an automobile interior material. It may be a molded article for use. Conversely, the adhesive body may be an automobile interior material, the first base material may be a molded article for automobile interiors, and the second base material may be a skin material.
  • An example of a method for manufacturing an automobile interior material is to apply the hot melt adhesive composition of the present disclosure to the back surface of a skin material (for example, the foamed layer surface of the skin material), and prepare a hot melt adhesive layer-containing skin material (pre-coated skin material).
  • Step of obtaining After reactivating the obtained pre-coated skin material with a far-infrared heater etc. and melting the hot melt adhesive layer, the skin material and the molded article for automobile interior are crimped together via the hot melt adhesive layer.
  • the process may include a step of causing Furthermore, a curing step for crystallizing the hot melt adhesive layer may be included.
  • the back surface of the skin material means the surface that faces the molded product for automotive interior when the skin material and the molded product for automotive interior are bonded together.
  • Component A ⁇ A-1: VERSIFY4200 manufactured by Dow Chemical Company (melting point 84°C, Shore A hardness 94, propylene/ethylene copolymer)
  • ⁇ A-2 VERSIFY3000 manufactured by Dow Chemical Company (melting point 108°C, Shore A hardness 96, propylene/ethylene copolymer)
  • Component B ⁇ B-1: VESTOPLAST792 manufactured by Evonik (softening point 108°C, propylene-ethylene-butene copolymer)
  • ⁇ B-2 RT2585 manufactured by REXTAC (softening point 132°C, propylene/ethylene copolymer)
  • Component C ⁇ C-1: Viscol 660-P manufactured by Sanyo Chemical Industries, Ltd.
  • YS resin PN1150 softening point 115°C, terpene type
  • ⁇ D-4 YS Polyster T145 manufactured by Yasuhara Chemical Co., Ltd. (softening point 145°C, terpene phenol type)
  • Component E ⁇ E-1: BASF Irganox 1010 (melting point 110°C, hindered phenol type)
  • E-2 Irgafos 168 manufactured by BASF (melting point 183°C, phosphorus type)
  • Component F ⁇ F-1: Calcium carbonate 300 mesh product manufactured by Shiraishi Calcium Co., Ltd.
  • sample 1 for adhesion test The above adhesive was applied to the surface of the skin material (TPO/PPF, total thickness 4 mm) at 180° C. using a roll coater so that the adhesive layer was 100 g/m2. Next, within one day after applying the adhesive, this skin material was heated with a far-infrared heater to a temperature of 160°C or higher, then immediately stacked on an aluminum plate (1 mm thick) and pressed under 0.1 MPa for 15 seconds. A laminate (sample 1 for adhesion test) was obtained.
  • sample 2 for adhesion test The above adhesive was applied to the surface of the skin material (TPO/PPF, total thickness 4 mm) at 180° C. using a roll coater so that the adhesive layer was 100 g/m2. Next, within one day after applying the adhesive, this skin material was heated with a far-infrared heater to a temperature of 160°C or higher, then immediately stacked on a PP board (thickness 2 mm) and pressed under 0.1 MPa and 15 seconds. A laminate (sample 2 for adhesion test) was obtained.
  • the hot melt adhesive composition of the present disclosure can be used, for example, as a solvent-free adhesive without VOC emissions, and has excellent adhesion and heat resistance to resin base materials, especially olefin base materials.
  • the workability allows for easy peeling from the mold (for example, when bonded using a vacuum forming method), it can be suitably used as an adhesive for automobile interiors.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un adhésif thermofusible qui contient une polyoléfine cristalline (A) ayant une dureté Shore A de 80 ou plus, une polyoléfine amorphe (B), et une cire de polypropylène (C), la quantité de la cire de polypropylène (C) étant de 60 parties en poids à 300 parties en poids pour un total de 100 parties en poids de la polyoléfine cristalline (A) et de la polyoléfine amorphe (B), qui a une bonne adhésivité à des matériaux de base en résine, en particulier des matériaux de base en polyoléfine tels que le polypropylène, et a également une aptitude au façonnage (aptitude au démoulage) qui permet une libération facile à partir d'un moule en tant que composition adhésive thermofusible.
PCT/JP2023/022213 2022-06-29 2023-06-15 Composition adhésive thermofusible, matériau de surface pré-revêtu pour intérieur d'automobile, matériau intérieur d'automobile et procédé de production d'objet lié WO2024004673A1 (fr)

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JP2022104621A JP2024004788A (ja) 2022-06-29 2022-06-29 ホットメルト接着剤組成物、自動車内装用プレコート表皮材、自動車内装材、及び接着体の製造方法

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009057397A (ja) * 2007-08-29 2009-03-19 Sanyo Chem Ind Ltd 難接着基材用ホットメルト接着剤
JP2013231114A (ja) * 2012-04-27 2013-11-14 Henkel Japan Ltd 電力機器用ホットメルト接着剤
JP2019521219A (ja) * 2016-07-01 2019-07-25 エイチ．ビー．フラー カンパニー 速い硬化時間を示すプロピレンポリマー系ホットメルト接着剤組成物及びそれを含む物品
WO2020050225A1 (fr) * 2018-09-04 2020-03-12 出光興産株式会社 Composition de résine thermoplastique et adhésif thermofusible
JP2020117605A (ja) * 2019-01-23 2020-08-06 ヘンケルジャパン株式会社 ホットメルト組成物
JP2020117606A (ja) * 2019-01-23 2020-08-06 ヘンケルジャパン株式会社 ホットメルト組成物
WO2020246063A1 (fr) * 2019-06-06 2020-12-10 昭和電工マテリアルズ株式会社 Composition adhésive thermofusible

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009057397A (ja) * 2007-08-29 2009-03-19 Sanyo Chem Ind Ltd 難接着基材用ホットメルト接着剤
JP2013231114A (ja) * 2012-04-27 2013-11-14 Henkel Japan Ltd 電力機器用ホットメルト接着剤
JP2019521219A (ja) * 2016-07-01 2019-07-25 エイチ．ビー．フラー カンパニー 速い硬化時間を示すプロピレンポリマー系ホットメルト接着剤組成物及びそれを含む物品
WO2020050225A1 (fr) * 2018-09-04 2020-03-12 出光興産株式会社 Composition de résine thermoplastique et adhésif thermofusible
JP2020117605A (ja) * 2019-01-23 2020-08-06 ヘンケルジャパン株式会社 ホットメルト組成物
JP2020117606A (ja) * 2019-01-23 2020-08-06 ヘンケルジャパン株式会社 ホットメルト組成物
WO2020246063A1 (fr) * 2019-06-06 2020-12-10 昭和電工マテリアルズ株式会社 Composition adhésive thermofusible

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